arXiv subjects
Publications and source records attributed to Venkatraman Gopalan.
Tables of crystallographic properties of double antisymmetry space groups, including symmetry element diagrams, general position diagrams, and positions, with multiplicities, site symmetries, coordinates, spin and roto vectors are presented.
We proved the existence of a universal flexo-antiferrodistortive coupling as a necessary complement to the well-known flexoelectric coupling. The coupling is universal for all antiferrodistortive systems and can lead to the formation of incommensurate, spatially-modulated phases in multiferroics. Our analysis can provide a self-consistent mesoscopic explanation for a broad range of modulated domain structures observed experimentally in multiferroics.
The structural and electronic recovery pathways of a photoexcited ultrathin VO2 film at nanosecond time scales have been studied using time-resolved x-ray diffraction and transient optical absorption techniques. The recovery pathways from the tetragonal metallic phase to the monoclinic insulating phase are highly dependent on the optical pump fluence. At pump fluences higher than the saturation fluence of 14.7 mJ/cm2, we observed a transient structural state with lattice parameter larger than that of the tetragonal phase, which is decoupled from the metal-to-insulator phase transition. Subsequently, the photoexcited VO2 film recovered to the ground state at characteristic times dependent upon the pump fluence, as a result of heat transport from the film to the substrate. We present a procedure to measure the time-resolved film temperature by correlating photoexcited and temperature-dependent x-ray diffraction measurements. A thermal transport model that incorporates changes of the thermal parameters across the phase transition reproduces the observed recovery dynamics. The optical excitation and fast recovery of ultrathin VO2 films provides a practical method to reversibly switch between the monoclinic insulating and tetragonal metallic state at nanosecond time scales.
The phase diagram of a quantum paraelectric antiferromagnet EuTiO3 under an external electric field was calculated using Landau-Ginzburg-Devonshire theory. It was shown that the application of an external electric field E leads to the appearance of a ferromagnetic phase due to the magnetoelectric coupling. In particular, electric field application decreases the transition temperature TAFM to antiferromagnetic (AFM) phase and induces ferromagnetic (FM) phase, so that at some E field larger than the critical field (Ecr), TFM becomes higher than TAFM and the FM phase appears. Note that Ecr increases and magnetization decreases as the temperature increases. The value of the critical field Ecr = 0.40*10^6 V/cm we calculated appeared close to the value Ecr = 0.5*10^6 V/cm obtained recently by Ryan et al. with the help of density functional theory for EuTiO3 film under a compressive strain produced by substrate. At the fields E >0.83*10^6 V/cm, AFM disappears for all considered temperatures and so FM becomes the only stable magnetic phase. We find that ferromagnetic phase can be induced by an E-field in other paraelectric antiferromagnet oxides with a positive AFM-type magnetoelectric (ME) coupling coefficient and negative FM-type ME coupling coefficient. In particular, the critical E-field was estimated for another paraelectric antiferromagnet Sr0.7Ba0.3MnO3 as 0.2x10^5V/cm at 0 K. Analysis of the dependence of magnetization and antimagnetization on the external electric field and the polarization induced by the field, which yields the magnetoelectric coupling, is reported. The results show the possibility to control multiferroicity, including the FM and AFM phases, with help of an electric field application.
Rotation-reversal symmetry was recently introduced to generalize the symmetry classification of rigid static rotations in crystals such as tilted octahedra in perovskite structures and tilted tetrahedral in silica structures. This operation has important implications for crystallographic group theory, namely that new symmetry groups are necessary to properly describe observations of rotation-reversal symmetry in crystals. When both rotation-reversal symmetry and time-reversal symmetry are considered in conjunction with space group symmetry, it is found that there are 17,803 types of symmetry, called double antisymmetry, which a crystal structure can exhibit. These symmetry groups have the potential to advance understanding of polyhedral rotations in crystals, the magnetic structure of crystals, and the coupling thereof. The full listing of the double antisymmetry space groups can be found in the supplemental materials of the present work and online at our website: http://sites.psu.edu/gopalan/research/symmetry/
Using Landau-Ginzburg-Devonshire theory and phase field modeling, we explore the complex interplay between the long-range structural order parameter (oxygen octahedron rotations) and polarization in EuxSr1-xTiO3 thin epitaxial films. In biaxially tensile strained films, we discover the presence of a low symmetry monoclinic phase with in-plane ferroelectric polarization that is stabilized by antiferrodistortive oxygen octahedra tilts. The monoclinic phase is stable in a wide temperature range, and is characterized by the large number of energetically equivalent polar and structural twin domains, which stimulates easy twinning of the film and thus enhances its effective piezoelectric response. The flexoelectric coupling and rotostriction give rise to additional spontaneous polarization, piezo- and pyro-electricity in the ferroelastic twin boundaries.
Electronic and structural phenomena at the twin domain wall-surface junctions in the ferroelastic materials are analyzed. Carriers accumulation caused by the strain-induced band structure changes originated via the deformation potential mechanism, structural order parameter gradient, rotostriction and flexoelectric coupling is explored. Approximate analytical results show that inhomogeneous elastic strains, which exist in the vicinity of the twin walls - surface junctions due to the rotostriction coupling, decrease the local band gap via the deformation potential and flexoelectric coupling mechanisms. This is the direct mechanism of the twin walls static conductivity in ferroelastics and, by extension, in multiferroics and ferroelectrics. On the other hand, flexoelectric and rotostriction coupling leads to the appearance of the improper polarization and electric fields proportional to the structural order parameter gradient in the vicinity of the twin walls - surface junctions. The "flexo-roto" fields leading to the carrier accumulation are considered as indirect mechanism of the twin walls conductivity. Comparison of the direct and indirect mechanisms illustrates complex range of phenomena directly responsible for domain walls static conductivity in materials with multiple order parameters.
Theoretical analysis based on the Landau-Ginzburg-Devonshire (LGD) theory is used to show that the joint action of flexoelectric effect and rotostriction leads to a large spontaneous in-plane polarization (~ 1-5 muC/cm2) and pyroelectric coefficient (~10^-3 C/m2K) in the vicinity of surfaces of otherwise non-ferroelectric ferroelastics, such as SrTiO3, with static octahedral rotations. The origin of the improper polarization and pyroelectricity is an electric field we name flexo-roto field whose strength is proportional to the convolution of the flexoelectric and rotostriction tensors with octahedral tilts and their gradients. Flexo-roto field should exist at surfaces and interfaces in all structures with static octahedral rotations, and thus it can induce surface polar states and pyroelectricity in a large class of otherwise nonpolar materials.
Theoretical analysis based on the Landau-Ginzburg-Devonshire (LGD) theory is used to show that the product effect of flexoelectricity and rotostriction can lead to a spontaneous polarization in the vicinity of antiphase boundaries, ferroelastic twin walls, surfaces and interfaces in the octahedrally tilted phase of otherwise non-ferroelectric perovskites such as CaTiO3, SrTiO3, and EuTiO3. As an example, we numerically demonstrate a large spontaneous polarization on the order of 1-5muC/cm2 at the SrTiO3 antidistortive phase boundaries at temperatures lower than the antiferrodistortive structural phase transition temperature of ~105 K
The antiferrodistortive (AFD) structural transitions of calcium titanate (CaTiO3) at ambient pressure have been extensively studied during the last few years. It is found none of the AFD polymorphs is polar or ferroelectric. However, it was recently shown theoretically and later experimentally confirmed that a ferroelectric transition in CaTiO3 can be induced by tensile strains. The ferroelectric instability is believed to be strongly coupled to the AFD soft modes. In this article, we present a complete thermodynamic potential for describing the coupling between the AFD and ferroelectric phase transitions. We analyzed the dependence of transition temperatures on stress and strain condition. Based on this potential, a (001) CaTiO3 thin film diagram was constructed. The results show good agreement with available experimental observations. The strong suppression of ferroelectric transition by the AFD transition is discussed.
Using Landau-Ginzburg-Devonshire theory we calculated numerically the static conductivity of both inclined and counter domain walls in the uniaxial ferroelectrics-semiconductors of n-type. We used the effective mass approximation for the electron and holes density of states, which is valid at arbitrary distance from the domain wall. Due to the electrons accumulation, the static conductivity drastically increases at the inclined head-to-head wall by 1 order of magnitude for small incline angles theta pi/40 by up 3 orders of magnitude for the counter domain wall (theta=pi/2). Two separate regions of the space charge accumulation exist across an inclined tail-to-tail wall: the thin region in the immediate vicinity of the wall with accumulated mobile holes and the much wider region with ionized donors. The conductivity across the tail-to-tail wall is at least an order of magnitude smaller than the one of the head-to-head wall due to the low mobility of holes, which are improper carries. The results are in qualitative agreement with recent experimental data for LiNbO3 doped with MgO.
For over a century, the structure of materials has been described by a combination of rotations, rotation-inversions and translational symmetries. By recognizing the reversal of static structural rotations between clockwise and counterclockwise directions as a distinct symmetry operation, here we show that there are many more structural symmetries than are currently recognized in right- or left-handed handed helices, spirals, and in antidistorted structures composed equally of rotations of both handedness. For example, though a helix or spiral cannot possess conventional mirror or inversion symmetries, they can possess them in combination with the rotation reversal symmetry. Similarly, we show that many antidistorted perovskites possess twice the number of symmetry elements as conventionally identified. These new symmetries predict new forms for "roto" properties that relate to static rotations, such as rotoelectricity, piezorotation, and rotomagnetism. They also enable symmetry-based search for new phenomena, such as multiferroicity involving a coupling of spins, electric polarization and static rotations. This work is relevant to structure-property relationships in all material structures with static rotations such as minerals, polymers, proteins, and engineered structures.
We studied the phase diagram of thin ferroelectric films with incommensurate phases and semiconductor properties within the framework of Landau-Ginzburg-Devonshire theory. We performed both analytical calculations and phase-field modelling of the temperature and thickness dependencies of the period of incommensurate 180 degree domain structures appeared in thin films covered with perfect electrodes. It is found that the transition temperature from the paraelectric into the incommensurate phase as well as the period of incommensurate domain structure strongly depend on film thickness, and surface and gradient energy contributions. The results may provide insight on the temperature dependence of domain structures in nanosized ferroics with inherent incommensurate phases.
While an ideal antiparallel ferroelectric wall is considered a unit cell in width (~0.5nm), we show using phase field modeling that the threshold field for moving this wall dramatically drops by 2-3 orders of magnitude if the wall were diffuse by only ~2-3nm. Since antiparallel domain walls are symmetry allowed in all ferroelectrics, and since domain wall broadening on nanometer scale is widely reported in literature, this mechanism is generally applicable to all ferroelectrics.
We study the effect of depolarization field related with inhomogeneous polarization distribution, strain and surface energy parameters on a domain wall profile near the surface of a ferroelectric film within the framework of Landau-Ginzburg-Devonshire phenomenology. Both inhomogeneous elastic stress and positive surface energy lead to the wall broadening at electrically screened surface. For ferroelectrics with weak piezoelectric coupling, the extrapolation length that defines surface energy parameter, affects the wall broadening more strongly than inhomogeneous elastic stress. Unexpectedly, the domain wall profile follows a long-range power law when approaching the surface, while it saturates exponentially in the bulk. In materials with high piezoelectric coupling and negligibly small surface energy (i.e. high extrapolation length) inhomogeneous elastic stress effect dominates.
Using confocal Raman and fluorescence spectroscopic imaging in 3-dimensions, we show direct evidence for Nd3+-Nd3+ interactions across grain boundaries (GBs) in Nd3+:YAG laser ceramics. It is clearly shown that Nd3+ segregation takes place at GBs leading to self-fluorescence quenching which affects a volume fraction as high as 20%. In addition, we show a clear trend of increasing spatial inhomogeneities in Nd3+ concentration when the doping levels exceeds 3 at%, which is not detected by standard spectrometry techniques. These results could point the way to further improvements in what is already an impressive class of ceramic laser materials.
The structure of a single antiparallel ferroelectric domain wall in LiNbO3 is quantitatively mapped by piezoelectric force microscopy (PFM) with calibrated probe geometry. The PFM measurements are performed for 49 probes with the radius varying from 10 to 300 nm. The magnitude and variation of the experimental piezoelectric coefficient across a domain wall matches the profiles calculated from a comprehensive analytical theory, as well as 3-dimensional finite element method simulations. Quantitative agreement between experimental and theoretical profile widths is obtained only when a finite disk-type tip radius that is in true contact with the sample surface is considered, which is in agreement with scanning electron microscopy images of the actual tips after imaging. The magnitude of the piezoelectric coefficient is shown to be independent of the tip radius, and the PFM profile width is linearly proportional to the tip radius. Finally we demonstrate a method to extract any intrinsic material broadening of the ferroelectric wall width. Surprisingly wide wall widths of 20- 200nm are observed.
Intrinsic domain wall width is a fundamental parameter that reflects bulk ferroelectric properties and governs the performance of ferroelectric memory devices. We present closed-form analytical expressions for vertical and lateral piezoelectric force microscopy (PFM) profiles for the conical and disc models of the tip, beyond point charge and sphere approximations. The analysis takes into account the finite intrinsic width of the domain wall, and dielectric anisotropy of the material. These analytical expressions provide insight into the mechanisms of PFM image formation and can be used for quantitative analysis of the PFM domain wall profiles. PFM profile of a realistic domain wall is shown to be the convolution of its intrinsic profile and resolution function of PFM.